3, 3, 5, 5-tetranitropiperidine



nie m P e This invention relates toa new series of nitropiperidinenitroalkyl compositions and their preparation.

This application is a continuationein-part of my application Serial No.392,474, filed November 16, 1953, now abandoned.

Inparticular, it relates to the nitropiperidine nitroalkyl compoundshaving the general formula: V a

wherein A is an alkylene radical a'nd R is a nitroalkyl, alkyl, nitro orhydrogen radical. 1

These compounds are-conveniently prepared and fare excellent highexplosives, and can be used in any.:con-' ventional explosive missile,projectile, rocket, or the like, as the main explosive charge, Anexample of such a missile is disclosed in United States Patent No.2,470,162, issued May 17, 1949. One way of using the high explosives ofthis invention in a device such as that disclosed in United StatesPatent No. 2,470,162, is to pack the crystalline explosive in powderform into the warhead of the missile. Alternatively, the crystals can befirst pelletized and thenpacked. A charge thus prepared is sufiicientlyinsensitive to withstand the shock entailed in the ejection of a shellfrom a gun barrel or from a rocket launching tube under the pressuredeveloped from ignition of a propellant charge, and can be caused toexplode on operation of an impactor time fuse-mechanism firing adetonating explosivesuch as lead azide or mercury fulminat'e.

The new nitropiperidine compounds of my invention are preparcdbycondensing 2,2,4,4-tetranitro-1,5-pentanediol with, a nitrofamine,in..accordan'ce with the follow! ing general reaction scheme:

wherein A is an alkylene radical andR is a nitroalkyl,

Alternatively, some of, the new compositions of my in ventio'n areprepared by condensing anitro alcohol havcorporation of I ice ing'anactivated hydroxyl group with tetranitropiperidine,

in accordance with the following general reaction scheme;

wherein R is a nitroalkyl, alkyl, nitro or hydrogen radical. 1 p t Thisreaction is essentially a Mannich type condensation and it has beendetermined that any alcohol having a hydroxyl group separated from adinitro-substituted carbon radical by no more thanone methylene groupwillreact in accordance with the reaction scheme'set forth above. This.results from, the fact that the hy-" droxy radical in such compounds isactivated the geminal dinitro grouping.

It will be appreciated that this alternativesynthesis is limited to thepreparation of compositions wherein the geminal dinitro grouping isseparated from the nitro-.

gen of the piperidine radical by a methylene radical.

In both of the above reactions, temperature is not critical although itis preferred to conduct the reaction at below room temperature in orderto provide more.

' efiective control.

The following examples are provided for purposes of illustration and arenotintended to in any way define V the limits of the invention.

EXAMPLE I Preparation of N-(2,2 ,2,trinitroethyl)-3,3,5,5-tetranitiopiperiqfinc A solution of 0 .3

solid. Two recrystallizations from benzene gave white crystals, M. P.163-168 C., I.S.=20 cm./2 kg. Analysis.-Calcd.for C HgN O Percent C,19.63; percent H, 1.88; percent N, 26.17. Found: 19.80; percent H, 1.79;percent N, 25.88. V V 5 EXAMPLE II p Preparation of N-(3,3,3 trinitropropyl) -3,3,5-,5-tetranitro-' piperia ine Y ture was stirred for 30minutes and cooledto 5 C.

The solid was collected, washed with water,'and dried; the yield was 3.3gm,-(M.P. 89-93" C.).' Three recrystallizations from concentrated nitricacid gave white plates (M.P. 142-144" C.,I.S.=25 'cm./2 kg.),

21.33; percent H, 2.29; percent N, 24.52. v

percent H, 2.28; percent N, 25:34. --Found:; Percent C Theexplosiveproperties of the com gm. of trinitroethanol, 0.3 gm/ of-3,3,5,5-tetranitropiperidine, and 15 .ml. of methanol wasrefluxed forsix hours, The solution Was coric,en-; trated in vacuo giving 0.45 gm.of a cream colored I Percent Q ou' nds prepared i: Table.

A wide variety of nitroalkylpiperidine compounds can be preparedaccording to my invention by proceeding in the manner set forth aboveand by reacting appropriate starting materials. For example,N-(3,3-dinitropentyl)-3,3,5,5-tetranitropiperidine is prepared byreacting Lamina-3,3-dinitropentane with 2,2,4,'4-tetranitro 1,5pentanediol; N 2,2,4,4 tetranitrobutyl)- 3,3,5,S-tetranitropiperidine isprepared by reacting 2,2, 4,4-tetranitro-l-butanol with3,3,5,S-tetranitropiperidine or by reactingl-amino-2,2,4,4-tetranitrobutane with 2,2,4,4 tetranitro 1,5pentanediol; N-(2,2,4,4-tetranitropentyl)-3,3,5,5-tetranitropiperidineis prepared by reacting 2,2,4,4-tetranitro-l-pentanol with3,3,5,5-tetranitropiperidine or by reacting1-amino-2,2,4,4-tetranitropentane with2,2,4,4-tetranitro-1,S-pentanediol; N-(2,2,4-trinitropentyl)3,3,5,5-tetranitropiperidine is prepared by reacting2,2,4-trinitro-1-pentanol with 3,3,5,5-tetranitropiperidine or byreacting 1-amino-2,2,4-trinitropentane with2,2,4,4-tetranitro-1,5-pentanediol;N-(3,3-dinitropropyl)-3,3,5,S-tetranitropiperidine is prepared byreacting l-amino-3,3-ditropropane with 2,2,4,4-tetranitro-1,5-pentanediol; and N-(1-methyl-3,3-dinitrobutyl)-3,3,5,5-

tetranitropiperidine is prepared by reacting 4,4-dinitro-2 pentanol with3,3,5,S-tetranitropiperidine or by reacting 2-amino-4,4-dinitropentanewith 2,2,4,4-tetranitro-1,5- pentanediol.

It will be appreciated that both higher and lower homologues of thesecompounds can be prepared in the identical manner without departing fromthe scope of my invention. All of these materials are usefulas highexplosives, as hereinbefore disclosed.

2,2,4,4-tetranitro-1,S-pentanediol used as a starting material in theamine condensation process of my invention is prepared according to themethod disclosed in assignees patent application Serial No. 371,150,filed July 29, 1953, and now abandoned. Tetranitropiperidine used as thestarting material in the nitro alcohol condensation according to myinvention is prepared by the method disclosed in my application SerialNo. 392,473, filed November 16, 1953, and now abandoned. -The nitroalcohols used in the alcohol-piperidine condensation reaction areprepared according to the methods' disclosed in assignees applicationsSerial Nos. 242,437, 371,149, 392,471, and 397,018, filed August 17,1951; July 29, 1953, November 16, 1953, and December 8, 195 3,respectively. Applications Serial Nos. 371,149 and 392,471 are nowabandoned.

The nitroamine salts useful in the alternative synthesis of my inventionare prepared according to the method of my United States patentapplication Serial No. 408,607, filed February 5, 1954, and nowabandoned.

Iclaim: 7

1. As new compositions of matter, the nitroalkyl tetranitropiperidinecompounds having the. general formula:

2. As new compositions of matter, the nitroalkyl tetranitropiperidinecompounds having the general formula;

wherein R'is a lower nitroalkyl radical and A a lower 1 I l 75 alkyleneradicals 4 3. As new compositions of matter, the nitroalkyltetranitropiperidine compounds having the general formula:

alkyl radical.

4. As new compositions of matter, the nitroalkyl tetranitropiperidinecompounds having the general formula:

-, wherein A is a lower alkylene radical.

5. As new compositions of matter, the nitroalkyl tetranitropiperidinecompounds having the general formula:

. wherein A is a lower alkylene radical.

6. As a new composition of matter,N-(2,2,2-trinitroethyl)-3,3,5,5-tetranitropiperidine having thestructural formula:

7. As a new composition of matter,N-(3,3,3-trinitropropyl)-3,3,5,5-tetranitropiperidine having thestructural formula:

8. As a new composition of matter,N-(3,3dinitropropyl)-3,3,5,5-tetranitropiperidine having the structuralformula:

9. As a new composition of matter, N-(2,2,4-trinitropentyl)-3,3,S,5-tetranitropiperidine having the structural formula:

. 1 10; Asa new compositionof matter,N-(2,2,4,4-tetranitropentyl)-3,3,5,5-tetranitropiperidine having thestructural formula:

11. As a new composition of matter,N-(2,2,4,4-tetranitrobutyl)-3,3,5,5-tetranitropiperidine having thestructural formula:

12. As a new composition of matter,N-(3,3-dinitropentyl)-3,3,5,5-tetranitropiperidine having the structuralformula:

13. The method of preparing N-nitroalkyl tetranitropiperidine compoundshaving the general formula:

(l cflr N 02 H20 N-CHr-C-R C-C z I TOa NOa Noz wherein R is a radicalselected from the group consisting of lower nitroalkyl, lower alkyl,nitro and hydrogen radicals, which comprises condensing3,3,5,5-tetranitropiperidine with a nitro alcohol having the generalformula:

wherein R is as defined above.

14. The method of preparing N-nitroalkyl tetranitro+ piperidinecompounds having the general formula:

wherein A is a lower alkylene radical and R is a radical selected fromthe group consisting of lower nitroalkyl, lower alkyl, nitro andhydrogen radicals, which comprises condensing2,2,4,4-tetranitro-1,5-pentanediol with a nitroalkyl amine having thegeneral formula:

N02 R(|)-ANH:|

No references cited.

1. AS NEW COMPOSITION OF MATTER, THE NITROALKYL TETRANITROPIPERIDINECOMPOUNDS HAVING THE GENERAL FORMULA: